THE  PREPARATION  OF  4 B.  CARBOXY  ETHENYL 
1 CHLORO  MERCURI  METHYL  1,  2,  DIHYDRO 
BENZO  FURAN  FROM  P.  HYDROXY 
BENZALDEHYDE 


By 

HORACE  BALDWIN  HUDDLE 

B.  S.  Georgetown  College,  1919 


THESIS 


SUBMITTED  IN  PARTIAL  FULFILLMENT  OF  THE  REQUIREMENTS 
FOR  THE  DEGREE  OF  MASTER  OF  SCIENCE  IN  CHEMISTRY 
IN  THE  GRADUATE  SCHOOL  OF  THE 
UNIVERSITY  OF  ILLINOIS,  1922 


URBANA,  ILLINOIS 


Digitized  by  the  Internet  Archive 
in  2016 


https://archive.org/details/preparationof4bc00hudd 


ff  ^(o 


UNIVERSITY  OF  ILLINOIS 


THE  GRADUATE  SCHOOL 


-May— 25— 


-192  2- 


I HEREBY  RECOMMEND  THAT  THE  THESIS  PREPARED  UNDER  MY 


SUPERVISION  BY Hor.ac.e_.  Baldwin  Huddle 


ENTITLED  The  Preparation  of- 


ivl  1 Chi  or- q 


Mere up i Methyl  X,  2 Dihydro  Benzo  Fur  an  from  E,  Hydroxy 

Benzaldehyde 

BE  ACCEPTED  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR 


THE  DEGREE 


.V.s-jof  Science 


In  Charge  of  Thesis 


Head  of  Department 


Recommendation  concurred  in* 


Committee 


on 


Final  Examination* 


•Required  for  doctor’s  degree  but  not  for  master’s 


4S9068 


ACKNOWLEDGMENT 


The  author  wishes  to  acknowledge  that  this  re- 
search was  undertaken  at  the  suggestion  of  and  was 
carried  out  under  the  kind  and  helpful  direction  of 
Dr.  Roger  Adams. 


TABLE  OP  CONTENTS 


Page 

I  Introduction  ---------------------  1 

II  Historical  and  Theoretical  --------------  2 

1.  (a)  Preparation  of  Para  Cumaric  Acid  ------  2 

(h)  Properties  of  Para  Cumaric  Acid  ------  4 

2.  Preparation  and  Properties  of  the  Methyl  - - 

Ester  of  Para  Cumaric  Acid  ---------  5 

3.  Preparation  of  Phenyl  Allyl  Ethers  -----  5 

4.  Preparation  of  Allyl  Phenols  --------  7 

5.  The  Reaction  with  Mercury  - - -------  7 

III  Experimental  ---------------------  9 

1.  Preparation  of  Para  Cumaric  Acid  ------  9 

2.  Preparation  of  the  Methyl  Ester  of  Para 
Cumaric  Acid  ----------------  ll 

3.  Preparation  of  the  Allyl  Ether  of  Para 
Hydroxy  Methyl  Cinnamate  ----------12 

4.  Preparation  of  Para  Hydroxy,  Meta  Allyl 
Methyl  Cinnamate  --------------13 

5.  Preparation  of  Para  Hydroxy  Meta  Allyl 

Cinnamic  Acid  ---------------  14 

6.  The  Reaction  with  HgCl2  ----------  15 

IV  Summary  -----------------------  16 

V  Bibliography  --------------------  17 


1 


INTRODUCTION 

It  was  found  in  this  laboratory  that  mercuric  chloride  v/ould  re- 
act with  ortho  allyl  phenols  to  give  chloro  mercuri  dihydro  benzo 
Curanes.  The  purpose  of  this  research  was  to  prepare  such  a deriva- 
tive which  would  be  alkali  soluble  in  hope  that  it  might  be  a useful 
drug.  The  particular  carboxyl  bearing  group  introduced  was  the  acry- 
lic acid  radical.  The  order  of  procedure  was  first  to  prepare  para 
hydroxy  cinnamic  acid  from  para  hydroxy  benzaldehyde • The  acid  was 
then  esterified  with  methyl  alcohol  giving  para  hydroxy  methyl  cinna- 
mate.  Next  in  order  the  allyl  ether  was  prepared  and  rearranged  into 
the  allyl  phenol  according  to  Claisen* . Lastly  the  mercury  was  in- 
troduced into  the  molecule. 


P.  Hydroxy  Benzaldehyde 
)CH2CH=CH2 


OH 

0 

0 

CH=CHCOGH 

ch=chcooch3 

Hydroxy  Cinnamic 

P.  Hydroxy  Methyl 

Acid 

Cinnamate 

ch2ch=ch2 

CH2CH=CH2 

ch=chcoochb 

si™ 

Hydroxy  Allyl 

P.  Hydroxy  Allyl 

Methyl  Cinnamate 


Cinnamic  Acid 


;h=chcooch3 

r 1 Ether  of  P.  Hydr< 
Methyl  Cinnamate 

HgCl 


4 Carboxy  Ethenyl  1 Chloro  Mercuri  Methyl  1,  2,  Dihydro  Benzo 
Fur  an 


' 


■ 


- 


■ 


f ■ ■ r 1 


;x 


■ 


. V 


Y. 


• • .•  -i  ■ " 


. 


1 V'  V r 


. 


i 


2 


II 


HISTORICAL  AMD  THEORETICAL 


1.  (a)  Preparation  of  Para  Cumaric  Acid. 

Preparation  of  para  hydroxy  cinnamic  acid  according  to 


Posner1.  Para  hydroxy  cinnamic  acid  can  be  easily  obtained  from  100 
grams  para  hydroxy  benzaldehyde,  160  grams  sodium  acetate,  fused, 
and  200  grams  acetic  anhydride.  The  mixture  was  boiled  with  a re- 
flux for  eight  hours  in  an  oil  bath.  The  yield  was  83  grams. 

Tiemann  and  Herzfeld2  describe  the  following  method;  eight  parts 
of  the  sodium  salt  of  para  hydroxy  benzaldehyde,  five  parts  of  pul- 
verized anhydrous  sodium  acetate  and  twenty  parts  of  acetic  anhy- 
dride are  gently  boiled  with  an  air  condenser  for  an  hour.  When 
cool  almost  the  whole  mass  solidifies  in  radiating  crystals.  By 
treatment  v/ith  water  the  sodium  acetate  and  the  excess  of  acetic  an- 
hydride are  dissolved  and  there  is  left  behind  a yellow  crystalline 
substance.  This  dissolves  in  alcohol,  ether,  acetic  acid  and  boiling 
water.  It  is  almost  insoluble  in  cold  water,  benzene  and  chloroform. 
It  sublimes  undecomposed  before  it  melts,  and  can  so  by  sublimation 
as  well  as  recrystallization  from  hot  water  be  obtained  in  pure  form. 
The  crystals  are  fine  white  needles  which  melt  at  195  uncorrected. 

The  melting  point  is  hard  to  observe  for  the  acetyl  para  hydroxy  cin- 
namic acid  seems  to  contract  and  begin  to  sublime  at  about  twenty 
degrees.  Boiling  with  potassium  hydroxide  changes  the  substance  into 
acetic  acid  and  para  cumaric  acid. 


CH  = CH  - COOH 


GH  = CH  - COOH 


3 


The  alkaline  solution  is  then  cooled  and  acidified  with  HClf  /hen 
the  para  cumaric  acid  separates  as  an  almost  red  colored  needle } The 
para  cumaric  acid  is  soluble  in  alcohol,  ether,  and  hot  water  and 
slightly  soluble  in  cold  water# 

An  article  by  Zinche  and  Leisse3  states  that  a description  of  this 
acid  ( para  cumaric)  was  given  by  Tieraann  and  Herzfeld  but  that  the 
authors  had  tried  the  method  described  and  obtained  only  very  poor 

yields.  By  making  slight  changes  in  the  quantities  used  the  yield 

o 

was  increased  to  80  /o  of  the  theoretical.  In  detail  the  method  was 
a3  follows:  50  grams  of  para  hydroxy  benzaldehyde,  80  grams  fused  so- 
dium acetate  and  150  grams  acetic  anhydride  were  intimately  mixed  in 
a round  bottom  flask  with  an  air  reflux  and  maintained  at  a gentle 
boil  on  a sand  bath  for  four  or  five  hours#  The  now  fluid  contents 
of  the  flask  were  poured  in  water  and  the  acetyl  para  hydroxy  cinna- 
mic acid  allowed  to  separate.  When  the  separation  was  complete  the 
material  was  filtered  on  a suction  filter  and  washed  with  water#  Then 
the  acetyl  para  hydroxy  cinnamic  acid  was  saponified  by  boiling  in 
dilute  NaOH.  Care  is  necessary  to  prevent  too  long  heating.  After 
the  alkaline  so  lution  has  cooled  it  is  poured,  drop  by  drop  into  an 
excess  of  somewhat  dilute  HC1.  The  solid  obtained  is  then  dissolved 
after  washing,  v/ith  water,  in  very  dilute  sodium  hydroxide  solution 
and  boiled  for  a longer  time  with  animal  charcoal.  The  acid  is  again 

separated  from  the  cooled  alkaline  solution  v/ith  HC1  as  above.  The 

o 

acid  is  recrystallized  from  hot  water  and  melts  at  206  C. 

S.  Gabriel  in  his  article  "Zur  Kenntiss  der  Hydrozimmt-  und  der 
Zimmts&ure4  describes  the  preparation  of  para  cumaric  acid  from  para 


4 

diazo  cinnamic  acid.  The  diazo  cinnamic  acid  was  dissolved  in  fifty 
carts  of  water  and  warmed  on  a water  hath.  The  solution  became  yel- 
low and  black  flakes  separated.  After  boiling  a half  hour  the  solu- 
tion was  filtered  and  a light  violet  filtrate  obtained  from  which, 

when  cooled,  crystals  were  obtained  that  on  recrystallization  from 

o 

hot  water  melted  at  200  . Although  the  melting  point  was  low  and 

o 

the  analysis  showed  a deficit  of  1-1.5  / carbon  Gabriel  was  sure 

o 

the  substance  was  pure  cumaric  acid  because  of  the  identity  of  the 
copper  salt  obtained  from  this  acid  with  that  prepared  by  Halswetz5. 

Halswetz  boiled  a hot  water  solution  of  alo£  with  dilute  sulfuric 
acid  for  an  hour.  He  then  extracted  with  ether  and  after  distilla- 
tion of  the  ether  recrystallized  the  residue  from  weak  alcohol.  Five 
pounds  of  alod  gave  24  grams  of  raw  product.  The  para  cumaric  acid 
is  colorless  and  crystallizes  in  shining  white  needles  from,  water. 
From  alcohol  the  needles  are  somewhat  longer.  Halswetz  prepared  the 
ammonium,  calcium,  copper,  and  silver  salts. 

(b)  Properties  of  Para  Cumaric  Acid . 

The  melting  point  of  para  cumaric  acid  is  given  at  206-207,  and 

o 

208  C.  It  is  non  volatile  with  steam  and  decomposes  on  distilling 
giving  C02  and  phenol.  Dissolves  slightly  in  cold  water  better  than 

in  alcohol.  It  is  insoluble  in  CHC13  and  CSs,  only  slightly  soluble 

o 

in  pure  ether  and  mixes  or  dissolves  in  10  /0  H2S04  with  heating. 

Para  cumaric  acid  is  soluble  in  dilute  ammonia  and  in  strong  alkali 
giving  a yellow  fluid  which  is  green  in  reflected  light.  In  the 
presence  of  CS2  and  in  the  cold  bromine  unites  with  the  acid.  The 
acid  can  be  separated  from  an  aldehyde  by  shaking  with  a water  solu- 


5 


tion  of  sodium  bisulfite* 


2.  The  Preparation  and  Properties  of  the  Methyl  Ester  of  Para  Cumaric 
Acid, 

In  Posner* s1 article  there  is  a statement  that  the  methyl  ester  of 

OH 

para  cumaric  acid  0 has  not  hitherto  been  described 

CH=CH  C-OCH3 

but  that  it  is  obtained  from  alkali  solution  with  carbonic  acid  and 
is  crystallized  from  methyl  alcohol  giving  a bright  sandlike  powder 

o 

which  melts  at  139-140  • 


^ 3 

The  article  by  Zinche  and  Leisse  states  that  the  methyl  ester 

can  be  obtained  in  the  usual  manner  with  HC1  and  can  be  recrystallizec 

o 

from  hot  water.  The  ester  forms  beautiful  white  needles  m.p.  137 
easily  soluble  in  ether,  acetic  acid,  alcohol  and  slightly  soluble  in 
benzene . 


Emil  Fischer  and  Osman  Nouri  prepared  the  methyl  ester  by  heating 
in  a pressure  flask  20  grams  of  para  hydroxy  cinnamic  acid,  50  grams 
methyl  alcohol  and  5 grams  concentrated  sulfuric  acid  for  four  hours 

at  a temperature  of  75-80  degrees.  After  dilution  with  150  cc.  of 

o 

water  the  solution  was  cooled  to  0 and  the  ester  allowed  to  separate. 
The  unchanged  acid  was  removed  by  washing  with  sodium  carbonate  solu- 
tion. The  ester  was  then  recrystallized  from  hot  water  giving  18 

o 

grams  or  83  /Q  of  theory  of  white  needlelike  crystals  m.p.  139-140 
corrected.  The  ester  was  readily  soluble  in  alcohol,  ether,  chloro- 
form, and  ethyl  acetate;  very  soluble  in  acetone  and  difficultly  solu- 
ble in  petroleum  ether. 


3.  The  Preparation  of  Phenyl  Allyl  Ethers . 

In  an  article  by  Claisen  and  Eiselb?  can  be  found  the  following 


. • 


. 


. 


. 

: 


. 

. 

. 


6 

statements  as  to  the  formation  of  phenyl  allyl  ethers.  The  phenol 
under  consideration  is  hoiled  in  a suitable  solvent,  usually  acetone, 
with  finely  pulverized  K2C03  and  allyl  bromide  on  a water  bath  till 
the  reaction  is  complete.  One  uses  a little  more  than  the  theoretical, 
amount  of  K2C03  and  CH2  = CH  - CH2Br  indicated  in  the  equation: 

ROH  + 03H5  Br  + K2C03  ROC3Hs  + KBr  + KHC03 

An  amount  of  acetone  equal  in  weight  to  that  of  the  phenol  is  used 
or  just  enough  to  make  a thick  porridge  with  the  potassium  salt  of 
the  phenol.  Too  much  acetone  is  to  be  avoided  since  it  gives  a solu- 
tion too  thick.  The  higher  boiling  methyl  ethyl  ketone  is  a better 
solvent  in  many  cases.  Acetone  is  not  practical  for  benzaldehyde 
since  it  condemns  with  it.  Alcohol  can  be  used  instead.  To  judge  of 
the  progress  and  the  end  of  the  reaction  a sample  is  removed  occa- 
sionally. This  sample  is  dissolved  in  petroleum  ether  and  extracted 
with  sodium  hydroxide  solution.  After  separation  the  alkaline  solu- 
tion is  neutralized  with  HG1  to  see  whether  any  phenol  separates. 

When  none  separates  the  reaction  is  complete.  The  time  needed  varies 
from  four  to  eight  hours.  After  the  reaction  is  complete  water  and 
petroleum  ether  are  added  to  the  flask.  The  ether  and  water  are 
separated  and  the  ether  extracted  well  with  NaOH  solution.  The  ether 
is  washed  with  water  and  dried  with  potash.  The  ether  is  volatilized 
from  a water  bath.  The  allyl  ether  remaining  as  an  oil  or  solid  is 
sufficiently  pure  for  use.  Further  purification  ma.y  sometimes  be  ac- 
complished by  vacuum  distillation. 

To  prepare  the  allyl  ether  of  para  hydroxy  ethyl  benzoate 

o c3h5 

0 which  is  analagous  to  the  allyl  ether  of  para 

C - 0C2H5 


. 


. 

•> 

. 


. 


- 

• 

. 

. 

■ 

*• 

• 

. 

* 

♦ 


7 


hydroxy  methylcinnamate 


CaH 


3iJ-5 


which  was  a necessary  inter- 


;h=cH-c-och3 

mediate  compound  in  this  synthesis  and  is  not  described  in  the  liter- 

para  hydroxy  allyl  ben- 


U 


ature  Claisen  used  250  grams  of 

■'cooc  H5 

zoate  with  210  grams  of  K2C03  and  185  grams  allyl  bromide  in  300 
grams  of  acetone.  The  mixture  was  boiled  six  hours  and  treated  as 

O . 

described  above.  The  yield  was  95  / • 


4.  Preparation  of  the  Allyl  Phenols  from  the  Allyl  Phenyl ethers. 

Claisen  found  that  by  heating  alkali  insoluble  allyl  phenylethers 
were  transformed  to  the  alkali  soluble  allyl  phenols;  the  allyl  group 
shifting  to  the  position  ortho  to  the  phenolic  hydroxyl  group. 

296  grams  of  the  allyl  ether  of  para  hydroxy  ethyl  benzoate  described 

o 

above  were  heated  in  an  oil  bath  at  220-250  for  one  half  hour.  Free 

boiling  did  not  occur,  however,  the  change  was  complete.  The  change 

o 

of  boiling  point  was  some  30  C.  from  that  of  the  ether. 


5.  The  Reaction  with  Mercury. 

The  problem  of  bringing  about  the  reaction  the  ortho  hydroxy 
meta  allyl  cinnamic  acid  was  not  difficult.  The  acid  was  prepared 
from  the  corresponding  methyl  ester  by  simple  hydrolysis  in  dilute 
NaOH.  Whitmore  states  that  common  cinnamic  acid  gives  no  compound 
with  mercuric  salts  from  which  all  of  the  mercury  cannot  be  precipi- 
tated by  acids.  No  reaction  was  expected  with  the  acrylic  acid 
radical.  It  has  been  discovered  in  this  laboratory  that  o allyl 
phenols  v/ill  react  with  mercuric  salts  to  give  chloro  mercuric,  1,2 
dihydro  benzo  furanes.  It  was  purposed  to  bring  about  such  a re- 
action between  mercuric  chloride  and  the  o, hydroxy  meta  allyl  cinna- 
mic acid. 


- 


•• 


■ 


. 


. 


* 


• • 


. . . 

. 


S’  r 


. . r ■ c. 


Ill 

EXPERIMENTAL 


9 


1.  The  Preparation  of  Para  Hydr oxy  Cinnamic  Acid  from  Para  Hydroxy 
Benz aldehyde . 

The  first  attempt  to  prepare  para  hydroxy  cumaric  acid  gave  very 

poor  yields.  Upon  investigation  it  was  found  that  the  acetic  anhy- 

o 

dride  used  contained  more  than  50  /©  of  the  low  boiling  anhydride. 

After  distillation  of  the  acetic  anhydride  and  refusion  of  the  sodium 

acetate  several  10  gram  samples  of  the  para  hydroxy  benzaldehyde  were 

tried  according  to  the  following  directions  which  were  formulated  by 

, :0H 

experimentation:  10  gram  of 


y/ 


16  gram  of  sodium  acetate 

o 


fused  and  30  gram  acetic  anhydride  which  boiled  at  or  above  137  v/ere 
placed  in  a 200  cc.  flask,  with  an  air  reflux  and  maintained  at  a 
gentle  boil  for  five  hours.  The  liquid  contents  of  the  flask  v/ere 
then  poured  with  stirring  into  800  cc.  water.  It  is  best  to  let  the 
precipitate  stand,  over  night  in  order  to  collect.  If  this  is  not 
done  it  is  sometimes  very  difficult  to  filter1.  The  precipitate  af- 
ter having  been  washed  successively  with  small  amounts  of  water  to 

o 

remove  any  acetic  acid  is  dissolved  in  250  cc.  of  10  /D  NaOH  and 
boiled  from  one  to  two  hours.  The  alkaline  solution  is  filtered  and 

cooled.  The  s olution  is  then  poured  drop  by  drop  with  stirring  into 

o 

300  cc.  10  /0  HC1  ice  cold.  Again  it  is  best  to  allow  the  precipi- 
tate to  stand  over  night.  After  washing  as  before  with  small  amounts 
of  water  filter  and  dissolve  by  boiling  in  500  cc.  water.  Let  the 
filtered  yellow  solution  cool  slowly  and  stand-  over  night.  There  is 

1.  The  filtrate  is  diluted  v/ith  water  to  precipitate  any  acetyl 

para  hydroxy  cinnamic  acid  present  in  case  the  concentration  of 
acetic  acid  is  too  strong. 


- 

. 


. 


. 


. 


) 


. 


. 

. 


. 


. 


. 


10 


o 

a loss  of  as  much  as  37  / of  the  crude  acid  upon  crystallization 
from  hot  water.  The  crystalline  acid  seems  mixed  with  a brownish 
red  gum  and  long  boiling  seems  to  convert  some  of  this  gum  by  solu- 
tion and  crystallization  into  the  crystalline  form.  Better  results 
are  obtained  if  the  sodium  acetate,  finely  pulverized,  is  dissolved 
in  the  acetic  anhydride,  as  far  as  possible  and  just  brought  to  a 
boil.  If  the  mixture  is  allowed  to  stop  boiling  and  the  flame  is 
removed  when  the  para  hydroxy  benzaldehyde  is  added,  the  boiling 


recommences  from  the  heat  of  reaction  and  will  continue  for  fifteen 


minutes 

without  the  flame. 

It  was  suggested 

that  I 2 

might  act 

as  a 

catalyst  for 

this  reaction. 

This  work  failed  to  verify  such  a 

con- 

elusion 

• 

No.  Grams 

Diluted  with 

Recrystallized 

Catalyst 

Yield 

M.P. 

CH 

c c « H 2 0 

from  cc . Ha0 

c=o 

H 

o 

1. 

25 

52  /„ 

206 

2. 

10 

800 

500 

la 

52°/0 

206 

3. 

10 

800 

500 

-- 

52°/0 

206 

4. 

10 

800 

500 

la 

67°/o 

206 

5. 

10 

800 

500 

-- 

o . 

68  /o 

206 

6 • 

10 

800 

500 

Is 

68°/0 

205 

7. 

10 

800 

500 

-- 

o , 

76  /<> 

205 

8. 

100 

8000 

3000 

-- 

o . 

50  /„ 

206 

9. 

100 

8000 

3000 

-- 

O , 

80  /0 

206 

10. 

200 

13000 

13000 

-- 

° . 

43  / o 

206 

11. 

100 

8000 

3000 

-- 

52  /0 

206 

11 


Samples  (2,  3)  (4,  5)  and  (6,  7)  were  duplicates  and  in  all  details 
were  given  the  same  treatment.  Too  long  boiling  of  the  alkaline  solu- 
tion during  saponification  is  probably  the  cause  of  some  of  the  low 
yields.  Overheating  or  too  long  boiling  of  the  original  mixture  seems 
to  increase  the  amount  of  reddish  brown  gum.  Upon  three  recrystalli- 
zations from  hot  water  a pure  white  short  needle  was  obtained  which 

o 

nelted  slightly  above  206  G. 

2.  Preparation  of  the  Methyl  Ester  of  Para  Hydroxy  Cinnamic  Acid. 

The  first  method  used  in  preparation  of  the  ester  was:  5.6  grams 

o 

Df  puce  acid  were  dissolved  in  100  cc.  of  CH30H  containing  4 /0  dry 
IC1.  This  cherry  red  solution  was  refluxed  on  a water  bath  for  ten 
lours.  The  solution  was  poured  in  water  and  the  ester  filtered.  The 
field  was  insignificant. 

The  method  of  Fischer  and  Nouri  gave  the  best  results.  After 
several  trials  the  following  method  was  determined.  20  grams  of  the 
icid,  50  grams  of  absolute  methyl  alcohol  and  5 grams  concentrated 
:i2S04  were  put  in  a pressure  flask  and  maintained  at  a temperature  of 

o 

75-85  for  eight  hours.  The  liquid,  after  filtration  of  any  crystals 
which  may  separate,  is  poured,  into  a liter  of  ice  water.  The  precipi- 
tate is  filtered  and  washed  and  finally  dissolved  in  1 liter  of  hot 
water.  On  standing  over  night  white  needles  sometimes  more  than  an 
Lnch  long  separate.  It  was  thought  that  possibly  by  evaporation  of 
bhe  alcohol  water  filtrate  under  diminished  pressure  the  yield  could 
De  increased.  This  process  seemed  only  to  increase  the  amount  of  red- 
lish  brown  gum. 


. 

. 

. 

. 

: • 


. 

. 


12 

In  the  literature  mention  of  only  one  form  of  crystal  was  found. 
Upon  recrystallization  from  alcohol  hexagonal  plates  separated. 

These  plates  were  apparently  perfect  in  form  and  symmetry  and  when 

recrystallized  from  hot  water  assumed  the  familar  needle  like  form. 

o 

The  melting  points  of  both  forms  were  the  same,  namely  137  C.  An- 
other interesting  detail  was  noticed.  When  a pressure  flask  contain- 
ing the  charge  described,  above  is  allowed  to  stand  without  heating  a 
weight  of  crystals  equal  to  one  half  the  usual  total  yield  separates 
from  the  solution.  There  is  also  usually  present  a small  amount  of 
unchanged  acid. 


No. 

G • Ac id 
used 

h2so4 

G 

Alco 

hoi 

Time  of 
heating 

Temper- 

ature 

M.P. 

Yield 
o . 

Alcohol  Recrystal- 
diluted  lized  from 
with  cc.  cc.  water 
water 

1. 

20 

5.g 

50 

g 

6 

hrs 

75-80 

137 

25  /„ 

500 

cc . 1500  cc. 

2. 

18 

5.g 

45 

g 

6 

hrs 

75-80 

137 

34  /0 

500 

cc.  1000  cc. 

3. 

201 

10. g 

50 

g 

8 

hrs 

75-83 

137 

43  /o 

500 

cc  • 

4. 

201 

5.g 

50 

g 

8 

hrs 

83 

137 

39  /„ 

500 

cc . 1000  cc . 

5. 

60 

15. g 

150 

g 

4 

hrs 

75-80 

137 

34°/ o 

1500 

cc.  3000  cc. 

6 • 

116 

30. g 

400 

cc5 

hrs 

75-80 

137 

34°/0 

4000 

cc.  4000  cc. 

3. 

Preparation 

of  the 

Allyl  Ether  of 

Para 

Hydroxy  Methyl  Cinnamate. 

25.3  grams  of  methyl  ester  of  para  hydroxy  cinnamic  acid,  18. 
grams  allyl  bromide2,  21.  grams  K2C03  finely  pulverized  and  30  grams 


acetone  were  heated  on  a water  bath  for  thirty  minutes  over  a low 


1.  3,4  were  run  to  test  effect  of  acid.  From  these  the  filtrates 
were  evaporated  under  diminished  pressure  yielding  only  small 
amounts • 

2.  The  allyl  bromide  used  was  prepared  according  to  the  directions 
p.76.  University  of  Illinois  Bulletin.  Organic  Chemical  Re- 
agents, I. 


13 


flame.  The  temperature  was  then  allowed  to  rise  till  the  mixture 
boiled.  A forty  one  inch  condenser  was  necessary.  When  the  sodium 
hydroxide  extract  of  an  ether  solution  of  a sample  gave  no  phenol 
upon  neutralization  the  reaction  was  complete.  The  solid  (KsC03  + 
KBR)  was  filtered  and  washed  with  acetone.  The  washings  were  added 
to  the  filtrate.  The  acetone  was  then  distilled  off  and  the  yellow- 
ish red  oil  poured  with  stirring  in  400  cc ♦ of  water.  A creamy  white 

solid  separated  which  was  filtered  and  washed  with  water.  This  mater. 

O , 

ial  is  insoluble  in  10  /0  NaOH,  and  in  water.  It  is  soluble  in  al- 
cohol, very  soluble  in  ether,  less  soluble  in  petroleum  ether  and 

o 

soluble  in  CHC13.  The  crude  product  melted  64  uncorrected,  66.9 
corrected.  This  product  can  be  crystallized  from  an  alcohol  water 
solution  in  the  following  manner;  dissolve  the  material  in  just  a 
sufficient  amount  of  hot  alcohol.  Add  enough  hot  water  to  almost 
precipitate  and  let  cool  slowly.  Snow  white  glistening 

flakes  separate  w hich  melt  at  64.5  uncorrected  or  71.3  corrected. 

o . 

The  yield  on  sample  1.  was  85  / . Sample  2 consisting  of  50.6  g. 

o 

gave  92  / yield. 

4.  The  Preparation  of  Para  Hydroxy,  Meta  Allyl  Methyl  Cinnamate . 

The  crude  ester  described  above  was  placed  in  a round  bottomed 
flask  and  with  an  air  reflux  and  heated  in  an  oil  bath.  When  cooled 
the  reddish  bro wn  oil  was  dissolved  in  ether  and  extracted  succes- 

sively  with  small  amounts  of  10  / 0 NaOH.  The  alkaline  solution  was 

o 

then  poured  into  an  excess  of  10  /0  HC1  ice  cold.  After  filtering 
and  washing  the  dry  brown  powder  was  dissolved  in  d.ry  ether  and  dried 
for  fifteen  minutes  with  CaCl3.  When  poured  off  the  ether  was  evapo- 
rated the  last  portion  being  volatilized  in  a vacuum  desiccator.  A 


14 


o 

brown  powder  resulted  which,  was  soluble  10  /0  NaOH,  soluble  in  ace- 

o 

tone,  alcohol  and  ether.  Insoluble  in  water,  benzene,  HC1  10  / 0» 

o 

10  /o  NaHC05  and  chloroform.  This  product  was  not  obtained  in  crys- 
talline form  but  was  used  to  prepare  the  next  product  which  was  ob- 
tained in  crystalline  form. 


Allyl  ether 
used 

Time  of  heating 

Temperature 

Yield 

/N 

18 

1 hour 

235-245 

yJ 

89  / 

0 

25 

2 hours 

220-240 

O / 

64  / 

o 

25 

2 hours 

230 

80°/o 

5.  Preparation  of  Para  Hydroxy  Meta  Allyl  Cinnamic  Acid. 

This  reaction  was  a simple  hydrolysis  in  10  /0  NaOH  of  the  pro- 
duct obtained  above.  The  alkaline  solution  was  poured  in  an  excess 

o 

of  10  / HC1  ice  cold  and  the  precipitate  allowed  to  collect.  When 
washed  and  dried  it  is  dissolved  in  ether  and  extracted  with  NaHC03 

o 

solution  10  /D . This  solution  is  again  poured  into  an  acid  solution 
as  above.  The  washed  and  dried  precipitate  is  dissolved  in  alcohol 
and  almost  precipitated  with  hot  water.  The  solution  is  then  boiled 
till  a film  of  crystals  begin  to  cover  the  surface.  On  cooling  the 
acid  comes  down  as  short  white  needles.  An  oil  begins  to  collect  in 
the  bottom  of  the  beaker.  Pour  off  the  supernatant  liquid  with  the 
crystals  and  redissolve  the  oil  in  alcohol  repeating  the  process. 

The  crystals  melt  at  165  uncorrected  and  168  corrected.  They  are 
soluble  in  alcohol,  ether  and  slightly  soluble  in  CHC1S. 


* 


/ 


15 


. of 

CII 

CH  ~ CH  = CK2 

Time  of  hydrolysis 

Yield 

CH  = CHC  00CH3 

5.  g 

1 hour 

95°/ 

20.  g 

4 hours 

o 

77  / 

7.  g 

3 hours 

54  / 

6#  The  Reaction  with  HgCl?. . 

.5  grains  of  the  para  hydroxy  meta  allyl  cinnamic  acid  described 
above  were  dissolved  in  the  last  possible  amount  of  ethyl  alcohol, 

• 66  grains  of  HgCl3  were  likewise  dissolved,  and  the  two  solutions 
poured  together  and  evaporated  nearly  to  dryness,  A solid  separated 
leaving  a green  stain  on  the  sides  of  the  beaker.  The  solid  was 
washed  with  water  to  remove  the  excess  HgCla  and  with  alcohol  to  re- 
move the  unchanged  acid.  The  remaining  brown  homogenous  powder  was 
soluble  in  10  /0  NaOH  but  insoluble  in  water  or  alcohol  and  only 
slightly  if  at  all  soluble  in  ether,  no  melting  point  was  obtained. 


. 


. 


. 


IV 


16 


SUMMARY 

In  the  preparation  of  4 car  "boxy  ethenyl,  1 chloromercuri 

methyl,  1,  2 dihydro  benzo  furan  from  para  hydroxy  benzaldehyde  it 
was  necessary  to  prepare  para  hydroxy  cinnamic  acid  and  its  methyl 
ester,  both  of  which  were  described  in  the  literature,  and  also  the 
new  compounds  the  allyl  ether  of  para  hydroxy  methyl  cinnamate,  the 
para  hydroxy  meta  allyl  me thy J cinnamate,  and  para  hydro xy  meta 
allyl  cinnamic  acid.  Of  the  four  new  compounds  two  were  obtained 
in  crystalline  form.  Although  the  para  hydroxy  meta  allyl  methyl 
cinnamate  was  not  obtained  in  crystalline  form  the  acid  prepared 
from  it  was.  The  mercury  compound  differed  from  the  acid  from  which 
it  was  prepared  in  not  being  soluble  in  alcohol. 

A hitherto  undescribed  crystalline  form  of  the  methyl  ester  of 
para  hydroxy  cinnamic  acid  was  noted,  and  detailed  directions  formu- 
lated for  the  preparation  of  para  cumaric  acid  and  its  methyl  ester. 
It  was  also  noted  that  heat  was  unnecessary  to  produce  esterfication 
of  the  para  hydroxy  meta  allyl  cinnamic  acid. 


. 


. 


.. ! ' ' •' 


V 


17 


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